CN112909260B - Ternary cathode material and preparation method thereof - Google Patents

Ternary cathode material and preparation method thereof Download PDF

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CN112909260B
CN112909260B CN202110166802.XA CN202110166802A CN112909260B CN 112909260 B CN112909260 B CN 112909260B CN 202110166802 A CN202110166802 A CN 202110166802A CN 112909260 B CN112909260 B CN 112909260B
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reaction
layer
precursor
zirconium
manganese
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CN112909260A (en
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朱佳兵
蔡志炬
胡骐
刘俊文
陈祥斌
胡文理
蔡君瑶
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Dongguan HEC Tech R&D Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • H01L25/16—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof the devices being of types provided for in two or more different main groups of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. forming hybrid circuits
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
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Abstract

The invention relates to a ternary cathode material, which is spherical particles with hollow interiors and comprises the following components: a dense inner layer forming the inner hollow; and a porous outer layer. The invention also discloses a preparation method of the ternary cathode material. The ternary cathode material is prepared from a precursor with a four-layer structure, wherein in the four-layer structure, a loose layer and a compact layer are alternated mutually, the loose layer is oxidized, the compact layer is doped with zirconium, and primary crystal grains of different layers of the precursor are different in volume shrinkage in a sintering process, so that an internal hollow structure is formed.

Description

Ternary cathode material and preparation method thereof
Technical Field
The invention relates to a lithium ion battery anode material, in particular to a ternary anode material and a preparation method thereof.
Background
The nickel-cobalt-manganese (NCM) ternary cathode material has the advantages of high capacity, long service life, low cost, rich raw material sources and the like, can be applied to the field of small lithium batteries and power batteries, and is a lithium ion battery material with great application prospect.
At present, the nickel-cobalt-manganese ternary positive electrode material is mainly prepared by a coprecipitation method through a continuous reaction kettle, a mixed aqueous solution of soluble salts of nickel, cobalt and manganese is continuously added into the reaction kettle, the mixed aqueous solution is complexed with ammonia, the pH value is controlled through sodium hydroxide, coprecipitation is carried out under the protection of inert gas to obtain a hydroxide composite precipitate product, and the hydroxide composite precipitate product is washed with water, filtered and dried and is sintered with lithium salt at a high temperature to obtain the nickel-cobalt-manganese ternary positive electrode material.
In order to improve the rate capability of the nickel-cobalt-manganese ternary material and meet the requirement of a 48V start-stop system of a light-duty automobile, the hollow-structure ternary material is mostly adopted in the market at present. For example, CN105185979A provides a method for preparing a hollow-structure positive electrode material for a lithium ion battery, comprising the following steps: s1, preparing more than one of nickel salt, cobalt salt and manganese salt into metal salt solution; s2, adding a metal salt solution, a precipitator and a complexing agent into a reaction kettle, and performing coprecipitation by adopting a mode of controlling reaction temperature, reaction time and reaction pH value in a segmented mode to obtain a precursor with a loose core and a compact shell; and S3, uniformly mixing the precursor with a lithium source according to the molar ratio of the total metal content in the precursor to the lithium element of 1 (0.9-2.2), and then carrying out an auxiliary segmented temperature control calcination process to obtain the lithium ion battery anode material with a hollow structure.
However, the current cathode material with a hollow structure mainly has the following disadvantages:
1. the mechanical strength is low, and the pole piece is easy to break in the rolling stage, so that the side reaction is increased;
2. the pole piece compaction density is low, resulting in low cell volume energy density. Because the hollow ternary material has low mechanical strength, the hollow structure of the material is generally kept by reducing the rolling pressure, so that the compaction density of the pole piece is lower, and the volume energy density of the battery cell is further reduced.
Disclosure of Invention
In order to solve the problems of low mechanical strength, low pole piece compaction density, more side reactions and the like of a hollow structure ternary cathode material in the prior art, the invention provides the ternary cathode material with an internal hollow structure and an external porous structure, which improves the mechanical strength of the cathode material while ensuring the high rate performance of the cathode material, so that the ternary cathode material is not cracked in the rolling process of a pole piece, the pole piece compaction density is increased, and the volume energy density of a battery cell is further increased.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
in one aspect, the present invention provides a ternary cathode material, which is a spherical particle with a hollow interior, and includes: a dense inner layer forming the inner hollow; and a porous outer layer.
The average diameter of the spherical particles is 6-12 mu m, and the average diameter of the inner hollow accounts for 1/4-3/5 of the average diameter of the spherical particles.
Further, primary crystal grains of the ternary cathode material are radially arranged.
Furthermore, the ternary positive electrode material is doped with zirconium, and the doping amount of the zirconium is 0.08-0.3%. The doping amount is the proportion of the mass of the zirconium element in the total mass of the ternary cathode material.
Furthermore, the doping amount of the zirconium is 0.2-0.3%.
Further, the ternary cathode material is prepared from a precursor, the precursor is spherical particles with a four-layer structure, and the four-layer structure is respectively from inside to outside:
kernel: the material has a loose porous structure, the diameter is 2-3 mu m, and the material is composed of flaky primary crystal grains with the thickness of 8-12 nm and the length of 200-500 nm;
a first intermediate layer: the crystal has a compact structure, the thickness of the crystal is 1-2 mu m, and the crystal is composed of flaky primary crystal grains with the thickness of 80-300 nm and the length of 500-1000 nm;
a second intermediate layer: has a loose porous structure, has a thickness of 0.5-1 μm, is composed of flaky primary crystal grains with a thickness of 8-12 nm and a length of 200-500 nm, and;
a housing: has a compact structure, has a thickness of 0.5-1 μm, and is composed of flaky primary crystal grains with a thickness of 80-300 nm and a length of 500-1000 nm.
According to the invention, the inner core of the precursor is loose and porous by controlling the multilayer structure of the precursor, a hollow structure is formed after sintering, the first intermediate layer is compact and thick and is used as a supporting framework, the second intermediate layer and the shell are both thin, and the volume shrinks to a certain extent but is not hollow after sintering, so that the porous structure is formed. If the thickness of the second intermediate layer or the outer shell is too thick, it may result in difficulty in forming a porous structure on the surface of the sintered particles.
Further, the precursor is formed by general formula NixCoyMnzZrk(OH)2Wherein x is more than 0.3 and less than 0.7, y is more than 0.1 and less than 0.3, z is more than 0.1 and less than 0.3, and k is more than 0.001 and less than 0.003.
In the invention, zirconium is selected as the doping element because zirconium has little influence on the volume of the ternary material, so that the particle size after sintering is consistent with that of the precursor, and the conventional doping elements such as aluminum, magnesium, titanium, boron and the like can increase the unit cell volume of the ternary material, so that the pore volume of the hollow and the shell is reduced, and the rate capability of the material is reduced.
According to the invention, the hollow structure in the prior art is adjusted to be a hollow porous structure, the porous structure can shorten a lithium ion transmission path, maintain higher liquid retention amount, and maintain the high rate performance of the material, and in addition, the pressure can be uniformly dispersed, the mechanical strength of the material is improved, and a pole piece with higher compaction density can be prepared. The porous outer layer of the ternary cathode material is of an open porous structure, so that the electrolyte can be fully infiltrated, the inner surfaces of the holes can be coated, the side reaction between the material interface and the electrolyte can be reduced, and the cycle performance of the material can be improved.
The primary crystal grains of the ternary cathode material are radially arranged, and the directions of expansion and contraction of the primary crystal grains are consistent in the radial structure in the charge and discharge processes of the material, so that the internal stress of the material is released, and the structural stability of the material is improved.
On the other hand, the invention provides a preparation method of the ternary cathode material, which comprises the following steps:
(1) mixing a mixed metal salt solution containing nickel, cobalt and manganese, a complexing agent, a precipitator and an oxidant to enrich oxygen in a reaction solution, and controlling the reaction pH to be 12.0-13.0 to obtain a core product;
(2) mixing a mixed metal salt solution containing nickel, cobalt, manganese and zirconium, a complexing agent and a precipitating agent with the core product obtained in the step (1) to ensure that the reaction solution is poor in oxygen, and controlling the reaction pH to be 12.0-12.2 and less than the pH value obtained in the step (1) to obtain a double-layer structure product with a first intermediate layer;
(3) mixing a mixed metal salt solution containing nickel, cobalt and manganese, a complexing agent, a precipitator and an oxidant with the double-layer structure product in the step (2) to enrich oxygen in the reaction liquid, and controlling the reaction pH to be 9.5-10.5 to obtain a three-layer structure product with a second middle layer;
(4) mixing a mixed metal salt solution containing nickel, cobalt, manganese and zirconium, a complexing agent and a precipitating agent with the three-layer structure product obtained in the step (3) to ensure that the reaction liquid is poor in oxygen, and controlling the reaction pH to be 12.0-12.2 and less than the pH value obtained in the step (1) to obtain a precursor with a four-layer structure;
(5) and (5) sintering the precursor in the step (4) and lithium salt for the first time to obtain the ternary cathode material.
Further, in the steps (1) and (3), the mixed metal salt containing nickel, cobalt and manganese is at least one of sulfate, acetate, chloride or nitrate.
Further, in the steps (1) and (3), the concentration of the mixed metal salt solution containing nickel, cobalt and manganese is 0.5-3 mol/L, wherein the molar ratio of nickel salt, cobalt salt and manganese salt is x: y: z, wherein x is more than 0.3 and less than 0.7, y is more than 0.1 and less than 0.3, and z is more than 0.1 and less than 0.3.
In the present invention, the concentration of the mixed metal salt solution containing nickel, cobalt and manganese refers to the ratio of the total mole number of nickel salt, cobalt salt and manganese salt to the volume of the solution.
Further, in steps (2) and (4), the mixed metal salt solution containing nickel, cobalt, manganese and zirconium is obtained by adding a zirconium salt to the mixed metal salt solution containing nickel, cobalt and manganese in step (1) or (3), wherein the zirconium salt is at least one of zirconium sulfate, zirconium acetate, zirconium chloride and zirconium nitrate, and the adding amount of the zirconium salt is as follows: the mass of the zirconium element accounts for 0.2-0.5% of the total mass of the metal elements (nickel, cobalt and manganese).
In the above steps (2) and (4), if the pH is higher than that in the step (1), the crystal cannot grow.
In the steps (1) to (4), the complexing agent is one or more of sodium citrate, sodium acetate, ammonium sulfate, ammonia water and EDTA, and preferably ammonia water.
In a specific embodiment of the invention, the complexing agent is provided by 10-15 mol/L ammonia water.
In the steps (1) to (4), the precipitant is one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonium carbonate, and ammonia water, and preferably sodium hydroxide.
In a specific embodiment of the invention, the precipitant is provided by 5-10 mol/L sodium hydroxide solution.
Further, in the step (1) and the step (3), the oxidant is hydrogen peroxide or sodium peroxide, preferably hydrogen peroxide.
In a specific embodiment of the invention, the oxidizing agent is provided by a 30% by mass aqueous solution of hydrogen peroxide.
Further, in the step (1), the reaction temperature is 25-50 ℃.
Further, in the step (2), the reaction temperature is 55-70 ℃.
Further, in the step (3), the reaction temperature is 25-50 ℃.
Further, in the step (4), the reaction temperature is 55-70 ℃.
In the step (1), the primary crystal grains of the obtained core are fine and loose by controlling the high pH value of the reaction and the oxygen enrichment, and have larger volume shrinkage during sintering, thereby being beneficial to the formation of an internal hollow structure. The presence of the oxidizing agent further reduces the crystallinity of the core.
In step (2), the core is grown by controlling the reaction to a higher pH and oxygen depletion to obtain a first intermediate layer with thick primary grains and a dense primary grain size that is maintained during sintering. The presence of zirconium increases the crystallinity of the first intermediate layer, delaminating the precursor, the first intermediate layer acting as a supporting skeleton during sintering and the radial crystallinity of the crystals gradually increasing from the core to the first intermediate layer, so that the volume shrinkage of the core after sintering tends to form hollows.
In the step (3), the primary crystal grains are formed to be large and loose in size by controlling the low pH value of the reaction and oxygen enrichment, the volume shrinks to a certain degree during sintering, and the crystallinity of the material is further reduced by the existence of the oxidant. And (4) forming a porous outer surface layer by sintering by controlling the thickness of the second middle layer and the thickness of the shell to be 0.5-1 mu m, which is the same as the step (2).
Further, the above steps (1) to (4) are carried out in a reaction vessel.
Further, before the step (1), pumping a proper amount of reaction base liquid into the reaction kettle. The reaction base solution is prepared by the following method: sequentially pumping deionized water, a complexing agent and a precipitator into a reaction kettle, controlling the mass concentration of the complexing agent in a reaction base solution to be 0.2-1.0 g/L, controlling the pH to be 12.0-13.0, and controlling the temperature to be 25-50 ℃.
Further, in the step (4), after the reaction is finished, the operation of washing with alkali liquor is also included, which is specifically as follows:
washing with a first alkali liquor: filtering the coprecipitation reaction mixture, and placing the obtained filter cake in alkali liquor to be stirred and aged for 2 hours at the aging temperature of 45-65 ℃; preferably, the alkali liquor is a sodium hydroxide solution with the concentration of 2-4 mol/L;
second alkali liquor washing: and filtering the aged filter cake, washing the filter cake with alkali liquor at the temperature of more than 50 ℃, washing the filter cake with pure water until the conductivity of the filtrate is less than 100us/cm, drying the filter cake at the temperature of 100-110 ℃, sieving the filter cake, and removing magnetism to obtain the precursor with the four-layer structure.
In the invention, the content of the impurity sulfur in the precursor can be reduced to 300ppm by alkali liquor washing, and the content of the impurity sulfur can be further reduced by adopting alkali liquor washing step by step, thereby improving the cycle performance of the material.
Further, in the step (5), the lithium salt is one or more of lithium carbonate, lithium hydroxide, lithium nitrate and lithium acetate.
Further, in the step (5), the primary sintering is carried out in an oxygen or air atmosphere, and the temperature of the primary sintering is 700-1000 ℃.
Further, in the step (5), the molar ratio of the precursor to the lithium salt is 1: (1.0-1.1).
Further, in the step (5), after the primary sintering, the method further includes: carrying out secondary sintering on the ternary cathode material and the coating agent at 350-650 ℃; wherein the coating agent is one or more of oxides containing Al, B, W, Y or La elements.
Further, the coating amount of the coating agent is 0-0.5%. The coating amount refers to the proportion of the mass of the coating agent to the mass of the ternary cathode material.
The invention has the beneficial effects that:
1. the ternary anode material precursor is designed into a four-layer structure, a loose layer and a compact layer are mutually alternated, the loose layer is oxidized, the compact layer is doped with zirconium, primary crystal grains of different layers of the precursor are differently shrunk in volume in the sintering process, so that a structure with a hollow interior, a compact inner layer and a porous outer layer is formed, and the primary crystal grains are radially arranged.
2. The ternary cathode material provided by the invention has the advantages that the specific surface area is increased, the infiltration effect of electrolyte is improved, the liquid retention capacity of the material is increased, and the high rate performance of the material is kept. In addition, the porous structure can also uniformly disperse the pressure, the mechanical strength of the material is improved, and the pole piece with higher compactness can be prepared. The open pore structure of the outer layer of the material is beneficial to the full infiltration of electrolyte, and can also realize the coating of the inner surface of the pore, reduce the side reaction between the material interface and the electrolyte and improve the cycle performance of the material.
3. The primary crystal grains of the ternary cathode material are designed to be radially arranged, and the primary crystal grains of the ternary cathode material with the radial structure are expanded and contracted in the same direction in the charging and discharging processes, so that the internal stress of the material is released, and the structural stability of the material is improved.
Definition of terms
In the present invention, unless otherwise specified, the solvent of the "solution" is referred to as "deionized water".
All ranges cited herein are inclusive, unless expressly stated to the contrary.
The numbers in this disclosure are approximate, regardless of whether the word "about" or "approximately" is used. The numerical value of the number may have differences of 1%, 2%, 5%, 7%, 8%, 10%, etc. Whenever a number with a value of N is disclosed, any number with a value of N +/-1%, N +/-2%, N +/-3%, N +/-5%, N +/-7%, N +/-8% or N +/-10% is explicitly disclosed, wherein "+/-" means plus or minus, and a range between N-10% and N + 10% is also disclosed.
The following definitions, as used herein, should be applied unless otherwise indicated. For the purposes of the present invention, the chemical elements are in accordance with the CAS version of the periodic Table of elements, and the 75 th version of the handbook of chemistry and Physics, 1994. In addition, general principles of Organic Chemistry can be referred to as described in "Organic Chemistry", Thomas Sorrell, University Science Books, Sausaltito: 1999, and "March's Advanced Organic Chemistry" by Michael B.Smith and Jerry March, John Wiley & Sons, New York:2007, the entire contents of which are incorporated herein by reference.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can also be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety, unless a specific section is cited. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.
Drawings
FIG. 1 shows a schematic structural diagram of a precursor prepared in an embodiment of the present invention, wherein 1-core, 2-first intermediate layer, 3-second intermediate layer, 4-shell;
FIG. 2 shows a schematic structural diagram of a ternary cathode material in an embodiment of the invention, wherein 5-hollow, 6-dense inner layer, 7-porous outer layer;
FIG. 3 shows an SEM image of a ternary cathode material in example 2 of the present invention;
FIG. 4 shows an SEM image of a ternary cathode material in comparative example 2 of the present invention;
fig. 5 shows rate performance curves of the batteries in the examples of the present invention and comparative examples.
Detailed Description
The following description is of the preferred embodiment of the present invention only, and is not intended to limit the present invention, and any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
The preparation method of the ternary cathode material of the present invention is described in detail below, and the specific preparation process of the above steps (1) to (5) is as follows:
(1) preparation of the inner core
Sequentially pumping deionized water, a complexing agent and a precipitator into a reaction kettle, controlling the content of the complexing agent to be 0.2-1.0 g/L, controlling the pH to be 12.0-13.0, controlling the temperature to be 25-50 ℃, and controlling the dissolved oxygen of the water solution of the reaction kettle to be in a saturated state to serve as a reaction bottom solution. Continuously pumping mixed metal salt solution containing nickel, cobalt and manganese, complexing agent, precipitator and oxidant into a reaction kettle, controlling the pH value and reaction temperature to be unchanged, and suspending pumping of reaction raw materials when the diameter of a product is 2-3 mu m, so as to obtain a core product mixed solution.
Specifically, the pH may be enumerated as: 12.0, 12.1, 12.2, 12.3, 12.4, 12.5, 12.6, 12.7, 12.8, 12.9, 13.0, etc.
The temperatures can be enumerated as: 25 deg.C, 30 deg.C, 35 deg.C, 40 deg.C, 45 deg.C, 50 deg.C, etc.
The diameter of the inner core can be listed as: 2.0. mu.m, 2.1. mu.m, 2.2. mu.m, 2.3. mu.m, 2.4. mu.m, 2.5. mu.m, 2.6. mu.m, 2.7. mu.m, 2.8. mu.m, 2.9. mu.m, 3.0. mu.m, etc.
(2) Preparation of the first intermediate layer
And (2) introducing protective gas into the mixed liquid of the kernel product obtained in the step (1) to discharge oxygen in the reaction kettle, heating the mixed liquid to 55-70 ℃, adjusting the content of the complexing agent to 3.0-5.0 g/L, and adjusting the pH value of the aqueous solution of the reaction kettle to 12.0-12.2 and less than the pH value obtained in the step (1). Continuously pumping a mixed metal salt solution containing nickel, cobalt, manganese and zirconium, a complexing agent and a precipitator into a reaction kettle, controlling the pH value and the temperature to be unchanged, forming an intermediate layer on the surface of an inner core product, and suspending pumping of reaction raw materials when the thickness of a first intermediate layer is 1-2 mu m, so as to obtain a double-layer structure product mixed solution with the first intermediate layer.
Specifically, the pH may be enumerated as: 12.0, 12.1, 12.2, etc.
The temperatures can be enumerated as: 55 deg.C, 56 deg.C, 57 deg.C, 58 deg.C, 59 deg.C, 60 deg.C, 61 deg.C, 62 deg.C, 63 deg.C, 64 deg.C, 65 deg.C, 66 deg.C, 67 deg.C, 68 deg.C, 69 deg.C, 70 deg.C, etc.
The first intermediate layer thickness may be enumerated as: 1.0 μm, 1.1 μm, 1.2 μm, 1.25 μm, 1.3 μm, 1.4 μm, 1.5 μm, 1.6 μm, 1.7 μm, 1.8 μm, 1.9 μm, 2.0 μm, and the like.
(3) Preparation of the second intermediate layer
And (3) introducing oxygen into the mixed liquid of the double-layer structure product obtained in the step (2), controlling the dissolved oxygen of the water solution of the reaction kettle to be in a saturated state, adjusting the pH to 9.5-10.5, reducing the temperature to 25-50 ℃, and adjusting the content of the complexing agent to 0.2-1.0 g/L. Continuously pumping mixed metal salt solution containing nickel, cobalt and manganese, complexing agent, precipitator and oxidant into a reaction kettle, controlling the pH value and reaction temperature to be unchanged, and stopping pumping reaction raw materials when the thickness of the second middle layer is 0.5-1 mu m, so as to obtain the product mixed solution with the three-layer structure of the second middle layer.
Specifically, the pH may be enumerated as: 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3, 10.4, 10.5, etc.
The temperatures can be enumerated as: 25 deg.C, 30 deg.C, 35 deg.C, 40 deg.C, 45 deg.C, 50 deg.C, etc.
The second intermediate layer thickness can be enumerated as: 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1.0 μm, and the like.
(4) Preparation of four-layer structure precursor
And (4) introducing protective gas into the mixed liquid of the product with the three-layer structure obtained in the step (3) to discharge oxygen in the reaction kettle, heating the mixed liquid to 55-70 ℃, adjusting the content of the complexing agent to 3.0-5.0 g/L, and adjusting the pH value of the aqueous solution of the reaction kettle to 12.0-12.2. Continuously pumping mixed metal salt solution containing nickel, cobalt, manganese and zirconium, complexing agent and precipitator into a reaction kettle, controlling the pH value and reaction temperature to be unchanged, forming an intermediate layer on the surface of a core product, and stopping pumping reaction raw materials when the reaction is carried out until the thickness of a shell is 0.5-1 mu m, thereby obtaining precursor mixed solution. Filtering the precursor mixed solution, placing the obtained filter cake in alkali liquor, stirring and aging for 2h, wherein the aging temperature is 45-65 ℃, filtering the aged filter cake, washing the filter cake with the alkali liquor with the temperature of more than 50 ℃, washing the filter cake with pure water until the conductivity of the filtrate is less than 100us/cm, and then drying, sieving and demagnetizing the filter cake at the temperature of 110 ℃ to obtain the precursor with the four-layer structure.
Specifically, the pH may be enumerated as: 12.0, 12.1, 12.2, etc.
The temperatures can be enumerated as: 55 deg.C, 56 deg.C, 57 deg.C, 58 deg.C, 59 deg.C, 60 deg.C, 61 deg.C, 62 deg.C, 63 deg.C, 64 deg.C, 65 deg.C, 66 deg.C, 67 deg.C, 68 deg.C, 69 deg.C, 70 deg.C, etc.
The shell thickness can be enumerated as: 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1.0 μm, and the like.
(5) Preparation of ternary cathode material
And (3) mixing the precursor obtained in the step (4) with lithium salt, performing primary sintering at 700-1000 ℃ for 8-24 h in an oxygen or air atmosphere, and performing secondary sintering with a coating agent at 350-650 ℃ for 5-15 h to obtain the ternary cathode material.
Specifically, the temperature of the primary sintering may be listed as: 700 deg.C, 750 deg.C, 800 deg.C, 850 deg.C, 890 deg.C, 900 deg.C, 950 deg.C, 1000 deg.C, etc.
The temperature of the secondary sintering may be enumerated as follows: 350 deg.C, 400 deg.C, 450 deg.C, 500 deg.C, 550 deg.C, 600 deg.C, 650 deg.C, etc.
Embodiments of the present invention will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples were carried out under conditions described in the specification, under conventional conditions or under conditions recommended by the manufacturer, unless otherwise specified. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
In this embodiment, the preparation method of the ternary cathode material includes:
(1) weighing nickel sulfate, cobalt sulfate and manganese sulfate according to a molar ratio of 6:2:2 to prepare a mixed metal salt solution 1 with the total metal ion concentration of 1.3 mol/L. Adding zirconium sulfate into the mixed metal salt solution 1 to prepare a mixed metal salt solution 2, wherein zirconium accounts for 0.3% of the total metal elements, preparing 13mol/L ammonia water as a complexing agent, 8mol/L sodium hydroxide solution as a precipitator and hydrogen peroxide solution with the mass concentration of 30% as an oxidant.
(2) Adding pure water, a complexing agent and a precipitator into a reaction kettle in sequence to serve as reaction base liquid, introducing oxygen, heating the reaction base liquid to 45 ℃, adjusting the content of the complexing agent in the reaction base liquid to be 0.5g/L, adjusting the pH value to be 12.10, and stirring at the rotating speed of 800 rpm.
(3) And simultaneously, pumping mixed metal salt solution 1, complexing agent, precipitator and oxidant into the reaction kettle, maintaining the pH value of the water solution of the reaction kettle at 12.10 and the reaction temperature at 45 ℃, controlling the dissolved oxygen amount of the water solution of the reaction kettle in a saturated state, carrying out coprecipitation reaction to generate crystal nucleus, and finishing the pumping of the raw materials after the reaction is carried out until the particle size of a product is 3 microns, thereby finishing the preparation process of the kernel.
(4) Introducing nitrogen into the reaction kettle to discharge oxygen, heating the water solution of the reaction kettle to 65 ℃, adjusting the content of the complexing agent to 4.0g/L, and adjusting the pH of the water solution of the reaction kettle to 12.00. And pumping the mixed salt solution 2, the precipitator and the complexing agent, controlling the pH and the temperature until the particle size of the product grows to 6 mu m, and finishing the raw material pumping to finish the preparation process of the first intermediate layer.
(5) And introducing oxygen into the reaction kettle, adjusting the pH to 10.00, reducing the temperature to 45 ℃, pumping the mixed metal salt solution 1, the complexing agent, the precipitator and the oxidant until the particle size of the product grows to 7 mu m, and finishing the raw material pumping to finish the preparation process of the second intermediate layer.
(6) And introducing nitrogen into the reaction kettle to discharge oxygen, heating the water solution of the reaction kettle to 65 ℃, adjusting the content of the complexing agent to 4.0g/L, and adjusting the pH of the water solution of the reaction kettle to 12.00. Pumping mixed salt solution 2, precipitator and complexing agent, controlling pH and temperature, and finishing the pumping of the raw materials after the grain size of the product grows to 8 mu m, thereby completing the preparation process of the precursor.
(7) Filtering the slurry containing the precursor, placing the obtained filter cake into 2mol/L sodium hydroxide solution, stirring and aging for 2h, wherein the aging temperature is 50 ℃. Filtering the aged precursor, washing a filter cake with 0.4mol/L sodium hydroxide solution at 50 ℃, and washing with pure water until the conductivity of the filtrate is below 200 mu s/cm. And drying the washed precursor at 110 ℃, sieving and demagnetizing to obtain the precursor.
(8) And (3) mixing the precursor obtained in the step (7) with lithium carbonate according to a molar ratio of 1: 1.05 mixing, sintering at 890 ℃ in air atmosphere, and mixing with nano Al2O3And after uniformly mixing the particle coating agents, carrying out secondary sintering at 550 ℃ to obtain the ternary cathode material.
Example 2
In this example, the difference from example 1 is that the starting material pumping was terminated after the particle size of the product in step (5) had grown to 8 μm, and the starting material pumping was terminated after the particle size of the product in step (6) had grown to 10 μm, and the rest of the procedure was the same as in example 1.
Comparative example 1
In this comparative example, the difference from the examples is that: in the step (1), sodium metaaluminate is used to replace zirconium sulfate in the mixed metal salt solution 2 so that aluminum accounts for 0.3% of the total metal element mass, and the rest of the steps are the same as those in the example 1.
Comparative example 2
In this comparative example, the precursor was of a double-layer structure, and the obtained ternary positive electrode material was hollow but without a porous outer layer, and the specific preparation process included:
(1) adding pure water, a complexing agent and a precipitator into a reaction kettle in sequence to serve as reaction base liquid, introducing oxygen, heating the reaction base liquid to 45 ℃, adjusting the content of the complexing agent in the reaction base liquid to be 0.5g/L, adjusting the pH value to be 12.10, and stirring at the rotating speed of 800 rpm.
(2) And simultaneously, pumping mixed metal salt solution 1, complexing agent, precipitator and oxidant into the reaction kettle, maintaining the pH value of the water solution of the reaction kettle at 12.10 and the reaction temperature at 45 ℃, controlling the dissolved oxygen amount of the water solution of the reaction kettle in a saturated state, carrying out coprecipitation reaction to generate crystal nucleus, and finishing the pumping of the raw materials after the reaction is carried out until the particle size of a product is 3 microns, thereby finishing the preparation process of the kernel.
(3) Introducing nitrogen into the reaction kettle to discharge oxygen, heating the water solution of the reaction kettle to 65 ℃, adjusting the content of the complexing agent to 4.0g/L, and adjusting the pH of the water solution of the reaction kettle to 12.00. And pumping the mixed salt solution 2, the precipitator and the complexing agent, controlling the pH and the temperature until the particle size of the product grows to 6 mu m, and finishing the pumping of the raw materials.
(4) Filtering the slurry containing the precursor, placing the obtained filter cake into 2mol/L sodium hydroxide solution, stirring and aging for 2h, wherein the aging temperature is 50 ℃. Filtering the aged precursor, washing a filter cake with 0.4mol/L sodium hydroxide solution at 50 ℃, and washing with pure water until the conductivity of the filtrate is below 200 mu s/cm. And drying the washed precursor at 110 ℃, sieving and demagnetizing to obtain the precursor.
(5) And (3) mixing the precursor obtained in the step (4) with lithium carbonate according to a molar ratio of 1: 1.05 mixing, sintering at 890 ℃ in air atmosphere, and mixing with nano Al2O3And after uniformly mixing the particle coating agents, carrying out secondary sintering at 550 ℃ to obtain the ternary cathode material.
Performance testing
The ternary cathode materials obtained in the embodiments 1-2 and the comparative examples 1-2 are prepared into button cells for rate performance detection, and the test result is shown in fig. 5, so that the ternary cathode material provided by the application has better rate performance.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.

Claims (16)

1. A ternary positive electrode material, wherein the ternary positive electrode material is a spherical particle having a hollow interior, and comprises:
a dense inner layer forming the inner hollow; and a porous outer layer;
the ternary cathode material is prepared from a precursor, wherein the precursor is spherical particles with a four-layer structure, and the four-layer structure comprises from inside to outside:
kernel: the material has a loose porous structure, the diameter is 2-3 mu m, and the material is composed of flaky primary crystal grains with the thickness of 8-12 nm and the length of 200-500 nm;
a first intermediate layer: the crystal has a compact structure, the thickness of the crystal is 1-2 mu m, and the crystal is composed of flaky primary crystal grains with the thickness of 80-300 nm and the length of 500-1000 nm;
a second intermediate layer: has a loose porous structure, has a thickness of 0.5-1 μm, is composed of flaky primary crystal grains with a thickness of 8-12 nm and a length of 200-500 nm, and;
a housing: the crystal has a compact structure, the thickness of the crystal is 0.5-1 mu m, and the crystal is composed of flaky primary crystal grains with the thickness of 80-300 nm and the length of 500-1000 nm;
the compact structures of the first intermediate layer and the outer shell are doped with zirconium.
2. The ternary positive electrode material according to claim 1, wherein the spherical particles have an average diameter of 6 to 12 μm, and the average diameter of the hollow interior accounts for 1/4 to 3/5 of the average diameter of the spherical particles.
3. The ternary positive electrode material according to claim 1, wherein the primary crystal grains of the ternary positive electrode material are arranged radially.
4. The ternary positive electrode material according to claim 1, wherein the amount of doped zirconium is 0.08 to 0.3%.
5. The ternary positive electrode material according to claim 1, wherein the precursor is represented by the general formula NixCoyMnzZrk(OH)2Wherein x is more than 0.3 and less than 0.7, y is more than 0.1 and less than 0.3, z is more than 0.1 and less than 0.3, and k is more than 0.001 and less than 0.003.
6. A method of preparing a ternary positive electrode material according to any one of claims 1 to 5, characterized in that it comprises the following steps:
(1) mixing a mixed metal salt solution containing nickel, cobalt and manganese, a complexing agent, a precipitator and an oxidant to enrich oxygen in a reaction solution, and controlling the reaction pH to be 12.0-13.0 to obtain a core product;
(2) mixing a mixed metal salt solution containing nickel, cobalt, manganese and zirconium, a complexing agent and a precipitating agent with the core product obtained in the step (1) to ensure that the reaction solution is poor in oxygen, and controlling the reaction pH to be 12.0-12.2 and less than the pH value obtained in the step (1) to obtain a double-layer structure product with a first intermediate layer;
(3) mixing a mixed metal salt solution containing nickel, cobalt and manganese, a complexing agent, a precipitator and an oxidant with the double-layer structure product in the step (2) to enrich oxygen in the reaction liquid, and controlling the reaction pH to be 9.5-10.5 to obtain a three-layer structure product with a second middle layer;
(4) mixing a mixed metal salt solution containing nickel, cobalt, manganese and zirconium, a complexing agent and a precipitating agent with the three-layer structure product obtained in the step (3) to ensure that the reaction liquid is poor in oxygen, and controlling the reaction pH to be 12.0-12.2 and less than the pH value obtained in the step (1) to obtain a precursor with a four-layer structure;
(5) and (5) sintering the precursor in the step (4) and lithium salt for the first time to obtain the ternary cathode material.
7. The method according to claim 6, wherein the concentration of the mixed metal salt solution containing nickel, cobalt and manganese in the steps (1) and (3) is 0.5-3 mol/L.
8. The method according to claim 6, wherein the mass of the zirconium element in the mixed metal salt solution containing nickel, cobalt, manganese and zirconium in the steps (2) and (4) is 0.2-0.5% of the total mass of the metal elements.
9. The method according to claim 6, wherein the reaction temperature in the step (1) is 25 to 50 ℃.
10. The method according to claim 6, wherein the reaction temperature in the step (2) is 55 to 70 ℃.
11. The method according to claim 6, wherein the reaction temperature in the step (3) is 25 to 50 ℃.
12. The method according to claim 6, wherein the reaction temperature in the step (4) is 55 to 70 ℃.
13. The preparation method according to claim 6, wherein in the steps (1) and (3), the oxidant is hydrogen peroxide or sodium peroxide.
14. The method according to claim 6, wherein the lithium salt is one or more of lithium carbonate, lithium nitrate and lithium hydroxide.
15. The method according to claim 6, wherein the temperature of the primary sintering is 700 to 1000 ℃.
16. The method according to claim 6, further comprising, after the primary sintering: carrying out secondary sintering on the ternary cathode material and the coating agent at 350-650 ℃; wherein the coating agent is one or more of oxides containing Al, B, W, Y or La elements.
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